So-called advanced epoxide resins based on cyclohex-1-ylmethylenediphenol derivatives or bicyclo(2.2.1)hept-1-ylmethylenediphenol derivatives

ABSTRACT

The invention relates to compounds of the formula I or II ##STR1## in which A is a radical ##STR2## R 1  is hydrogen or methyl, R 2  is the radical of an aliphatic, cycloaliphatic, aromatic or araliphatic diol after both of the hydroxyl groups have been removed, R 3 , R 4 , R 5  and R 6  independently of one another are hydrogen, C 1  -C 6  alkyl, chlorine or bromine, R 7  is a radical of the formula III, IV, V or VI ##STR3## R 8 , R 10 , R 12  and R 14  are hydrogen, C 1  -C 6  alkyl or phenyl, R 9 , R 11 , R 13  and R 15  are hydrogen or C 1  -C 6  alkyl and the average value of n (number average) is a number from 1 to 20, it being possible for the radicals R 1  to R 15 , within a given molecule, to assume different meanings within the scope of the definitions given. 
     These compounds or also the epoxidized intermediates of the formula X ##STR4## in which R 1  to R 3  are defined above and R 7  is a radical of the formula IV or VI can be processed to give cured products having a high glass transition temperature and a low tendency to discoloration.

The present invention relates to so-called advanced epoxide resinsderived from special diphenols or from diglycidyl ethers based on thesephenols, to a process for the preparation of the special diphenols, tothe novel glycidyl ether intermediates and to curable mixturescontaining the so-called advanced derivatives and/or the intermediatesin combination with curing agents.

Cyclohex-1-ylmethylenediphenols are known from British Pat. No.1,024,012. Bicyclo[2.2.1]hept-1-ylmethylenediphenols are described inBritish Pat. No. 1,024,013. These compounds are employed, for example,as monomer components in the preparation of polycarbonates. Reactions ofthis type are described in British Pat. No. 1,024,011. The preparationof glycidyl ethers of hydroxylaryl-3,4-epoxycyclohexylmethanes isdescribed by B. M. Tkatschuk et al. (cf. Ref. Zh. Khim., 1985, Abstr.No. 19S419). The compounds prepared in this reference are low-molecularand accordingly have a relatively low viscosity.

For certain applications, for example laminates, oligomers having a morehighly built-up structure are advantageous.

A class of so-called advanced epoxide resins which are distinguished byadvantageous properties, compared with conventional so-called advancedepoxide resins based on bisphenol A, have now been found.

Thus the cured products from these novel resins as a rule have highglass transition temperatures; in addition products having only a slightdiscoloration are obtained when they are cured with imidazoleaccelerators.

The present invention relates to compounds of the formula I or II##STR5## in which A is a radical, ##STR6## R¹ is hydrogen or methyl, R²is the radical of an aliphatic, cycloaliphatic, aromatic or araliphaticdiol after both of the hydroxyl groups have been removed, R³, R⁴, R⁵ andR⁶ independently of one another are hydrogen, C₁ -C₆ alkyl, chlorine orbromine, R⁷ is a radical of the formula III, IV, V or VI. ##STR7## R⁸,R¹⁰, R¹² and R¹⁴ are hydrogen, C₁ -C₆ alkyl or phenyl, R⁹, R¹¹ R¹³ andR¹⁵ are hydrogen or C₁ -C₆ alkyl and the average value of n (numberaverage) is a number from 1 to 20, it being possible for the radicals R¹to R¹⁵, within a given molecule, to assume different meanings within thescope of the definitions given. R¹ is preferably hydrogen.

If R² is derived from an aliphatic diol, it is a linear orbranched-chain alkylene radical which can, if desired, be interrupted byoxygen or sulfur atoms and which can be substituted or unsubstituted.

Examples of substituents are chlorine and bromine.

Unsubstituted linear C₂ -C₂₀ alkylene radicals are preferred. Examplesof these are ethylene, trimethylene, tetramethylene, pentamethylene,hexamethylene, heptamethylene, octamethylene, decamethylene,dodecamethylene, tetradecamethylene, hexadecamethylene,octadecamethylene or eicosoamethylene.

Tetramethylene is particularly preferred.

The diol on which R² is based can, however, also be a poly-(oxyalkylene)glycol or a poly-(thioalkylene) glycol. The derivatives containingoxygen are preferred.

Examples of these are poly-(ethylene) glycol, poly-(propylene) glycol orpoly-(butylene) glycol having 2-60 monomer units.

If R² is derived from a cycloaliphatic diol, it is, for example, a diolhaving a cycloaliphatic ring containing 5-7 carbon atoms which can, ifappropriate, be part of an aliphatic chain or which can, if appropriate,carry substituents directly attached to the ring.

Examples of such radicals are cyclopentylene, cyclohexylene orcycloheptylene.

Cyclohexylene, particularly 1,3-cyclohexylene or 1,4-cyclohexylene, isparticularly preferred. Hexahydroxylylene is also of interest.

If R² is based on an aromatic diol, this radical is preferably derivedfrom a mononuclear of dinuclear phenol. Preferred examples of these are1,2-phenylene or, in particular, 1,3-phenylene or 1,4-phenylene and alsoradicals of the formula VII ##STR8## in which the free bonds arepreferably in the 3-position or 4-position relative to the bridge X, andX is a direct C--C bond or is selected from the group of radicalsconsisting of --CH₂ --, --CHCH₃ --, --C(CH₃)₂, --O--, --S--, --SO₂ -- or--CO--, m is an integer from 0 to 4, preferably 0, 1 or 2 and veryparticularly preferably 0, and R¹⁶ and R¹⁷ independently of one anotherare C₁ -C₆ alkyl, chlorine or bromine.

Preferred radicals R² are diphenylmethane-4,4'-diyl,diphenylether-4,4'-diyl, diphenylsulphone-4,4'-diyl and, veryparticularly, diphenyl-2,2-propylidene-4,4'-diyl. Xylylene is an exampleof R² as an araliphatic radical.

C₁ -C₆ alkyl radicals R³ to R⁶ and R⁸ to R¹⁷ can be linear or branched.Examples of these are methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, tert-butyl, n-pentyl or n-hexyl.

Linear C₁ -C₄ alkyl radicals, in particular methyl, are preferred.

Compounds of the formula I or II which are very particularly preferredare those in which R² is a radical of the formula VIIa ##STR9## and R³,R⁴, R⁵, R⁶ and R⁷ are as defined earlier in the text.

The radicals R³ to R⁶ and R⁸ to R¹⁵ are particularly preferablyhydrogen.

The compounds of the formula I or II are present, as a rule, as amixture of components of varying chain length. The average molecularweight (number average; determined by gel permeation chromatography) isat least as high as the molecular weight of the corresponding purecompound in which n is 1.

The average value of n is preferably a number from 1 to 10, veryparticularly from 1 to 5.

R⁷ is preferably a radical of the formula III or of the formula IV.Further preferred radicals R⁷ are the epoxidized types of the formula VIor especially V, in which R¹², R¹³, R¹⁴ and R¹⁵ are hydrogen.

The compounds of the formula I are derived from diphenols of the formulaVIII ##STR10## in which R³, R⁴, R⁵ and R⁶ are as defined earlier in thetext and R^(7') is a radical of the formula III or IV. These compoundsare known from the British Pat. Nos. 1,024,012 or 1,024,013 mentionedabove or can be prepared analogously to the procedures describedtherein.

The invention also relates, however, to a process for the preparation ofcompounds of the formula VIII wherein high yields are achieved. Thisprocess embraces the reaction of an aldehyde of the formula VIIIa

    V.sup.7' --CHO                                             (VIIIa),

in which R^(7') is as defined above, with a 4-molar to 8-molar excess,relative to the aldehyde, of a phenol of the formula VIIIb or of amixture of these phenols ##STR11## in which R^(a) and R^(b) are asdefined earlier in the text for R³, R⁴, R⁵ and R⁶ ; the processcomprises the use of a mononuclear aromatic hydrocarbon as the solventand of an aromatic sulfonic acid as the catalyst. If desired, a mercaptocompound can also be present in addition, for example thiolactic acid,mercaptoacetic acid or mercaptopropionic acid. A further increase in theyield can be achieved by this means.

As a rule, the reaction temperature is between -10° C. and the boilingpoint of the particular solvent (mixture), preferably between 0°-70° C.

Examples of suitable mononuclear aromatic hydrocarbons are benzene,toluene, ethylbenzene, cumene, xylene or chlorobenzene, particularlytoluene. It is also possible to employ mixtures.

Examples of suitable aromatic sulfonic acids are benzenesulfonic,toluenesulfonic or naphthalenesulfonic acids, but particularlytoluenesulfonic acid. It is also possible to employ mixtures.

The diphenols of the formula VIII in which R^(7') is, in addition, aradical of the formula V or VI can also be employed as curing agents forcurable epoxide resins, which is also a subject of the presentinvention.

The compounds of the formula I containing the unsaturated radicals R⁷ ofthe formula III or IV can be obtained in a manner known per se byreacting n moles of a diphenol of the formula VIII with n+1 moles of adiepoxide of the formula IX ##STR12## in which n, R1 and R2 are asdefined earlier in the text.

The compounds of the formula I containing the epoxidized radicals R⁷ ofthe formula V or VI can be obtained by epoxidizing a compound of theformula I containing unsaturated radicals R⁷ of the formula III or IV bymeans of a peracid in a manner known per se.

The epoxidation by means of a peracid can also be carried out in such away that only part of the unsaturated radicals of the formula III or IVis converted into the corresponding epoxide compound.

The compounds of the formula II are derived from diglycidyl ethers ofthe formula X ##STR13## in which R¹, R³, R⁴, R⁵, R⁶ and R⁷ are asdefined earlier in the text. These compounds are, therefore, diepoxideor triepoxide compounds, depending the nature of the radical R⁷.

The compounds of the formula X containing the radicals R⁷ of theformulae IV and VI are novel and also form a subject of the presentinvention.

The diepoxide compounds of the formula X can be obtained from thedipenols of the formula VIII in a manner known per se by reacting thelatter with epichlorohydrin or with β-methylepichlorohydrin.

The triepoxide compounds of the formula X can be obtained by reactingthe diglycidyl ethers of the formula X, containing unsaturated radicalsR⁷ of the formula III or IV with a peracid.

The compounds of the formula II containing unsaturated radicals R⁷ ofthe formula III or IV can be obtained in a manner known per se byreacting n moles of a diol of the formula XI

    HO--R.sup.2 --OH                                           (XI)

in which n and R² are as defined earlier in the text with n+1 moles of adiglycidyl ether of the formula X containing the radicals R⁷ of theformula III or IV.

The compounds of the formula II containing the epoxidized radicals R⁷ ofthe formula V or VI can be obtained (a) by reacting n+1 moles of thediglycidyl ether of the formula X in which the R⁷ s are radicals of theformula V or VI with n moles of a diol of the formula XI in a mannerknown per se or (b) by epoxidizing a compound of the formula IIcontaining unsaturated radicals R⁷ of the formula III or IV in a mannerknown per se by means of a peracid.

The epoxidation by means of a peracid can also be carried out in such away that only a part of the unsaturated radicals of the formula III orIV is converted into the corresponding epoxide compounds.

It is preferable to react n+1 moles of the diglycidyl ether of theformula X with n moles of the diphenol of the formula VIII and, ifappropriate, to epoxidize the product with a peracid.

In a further preferred embodiment of the process, n+1 moles of thediphenol of the formula VIII are reacted with n moles of the diglycidylether of the formula X and the product, if appropriate, is epoxidized bymeans of a peracid.

The so-called advancement of the diglycidyl ether IX with the diphenolVIII or of the diglycidyl ether X with the diol XI is carried outanalogously to known processes. So-called advancements of this type arecarried out in industry, for example in the synthesis of long-chaindiglycidyl ethers based on bisphenol, and are described in the "EpoxyHandbook" by Lee and Neville, chapters 2-9.

The epoxidation of olefinically unsaturated compounds by means ofperacids is also known and is described, for example, in the "EpoxyHandbook" by Lee and Neville, chapter 3.

The so-called advanced compounds of the formula I or II and also themonomeric starting materials for the so-called advancement reaction ofthe formula X can be employed in combination with curing agents ascurable mixtures.

The invention therefore also relates to a curable mixture containing

(a) at least one compound of the formula I or II,

(b) an amount of an epoxide curing agent adequate for curing the saidmixture, and

(c) if appropriate, a curing accelerator.

The invention also relates to a curable mixture containing

(a) at least one compound of the formula X in which R⁷ is a radical ofthe formula IV or VI,

(b) an amount of an epoxide curing agent adequate for curing the saidmixture, and

(c) if appropriate, a curing accelerator.

It is also possible, of course, to employ mixtures of the compounds I,II and/or X, or to use these compounds in combination with other knownepoxide resins.

The following should be mentioned as examples of additional epoxideresins which can be employed together with the compounds I, II and/or X:

(I) Polyglycidyl and poly-(β-methyglycidyl) esters which can be obtainedby reacting a compound containing at least two carboxyl groups in themolecule and epichlorohydrin or glycerol dichlorohydrin orβ-methylepichlorohydrin. The reaction is advantageously carried out inthe presence of bases.

Aliphatic polycarboxylic acids can be used as the compound containing atleast two carboxyl groups in the molecule. Examples of thesepolycarboxylic acids are oxalic acid, succinic acid, glutaric acid,adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid ordimerized or trimerized linoleic acid.

It is also possible, however, to employ cycloaliphatic polycarboxylicacids, for example tetrahydrophthalic acid, 4-methyltetrahydrophthalicacid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid.

It is also possible to use aromatic polycarboxylic acids, for examplephthalic acid, isophthalic acid or terephthalic acid.

(II) Polyglycidyl or poly-(β-methylglycidyl) ethers which can beobtained by reacting a compound containing at least two free alcoholichydroxyl groups and/or phenolic hydroxyl groups and a suitablysubstituted epichlorohydrin under alkali conditions, or in the presenceof an acid catalyst, with subsequent alkali treatment.

Ethers of this type are derived, for example, from acyclic alcohols,such as ethylene glycol, diethylene glycol and higher poly-(oxyethylene)glycols, propane-1,2-diol or poly(oxypropylene) glycols,propane-1,3-diol, butane-1,4-diol, poly-(oxytetramethylene) glycols,pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol,1,1,1-trimethylolpropane, pentaerythritol, sorbitol and also frompolyepichlorohydrins.

They are, however, also derived, for example, from cycloalphaticalcohols, such as 1,3-dihydrocyclohexane, 1,4-dihydroxycyclohexane,bis-(4-hydroxycyclohexyl)-methane, 2,2-bis-(4-hydroxycyclohexyl)-propaneor 1,1-bis-(hydroxymethyl)-cyclohex-3-ene, or they have aromatic nuclei,such as N,N-bis-(2-hydroxyethyl)-aniline orp,p'-bis-(2-hydroxyethylamino)-diphenylmethane.

The epoxide compounds can also be derived from mononuclear phenols, forexample from resorcinol or hydroquinone; or they are based onpolynuclear phenols, for example bis-(4-hydroxyphenyl)-methane,4,4'-dihydroxybiphenyl, bis-(4-hydroxyphenyl)-sulfone,1,1,2,2-tetrakis-(4-hydroxyphenyl)-ethane,2,2,-bis-(4-hydroxyphenyl)-propane,2,2,-bis-(3,5-dibromo-4-hydroxyphenyl)-propane and novolaks which can beobtained by subjecting aldehydes, for example formaldehyde,acetaldehyde, chloral or furfuraldehyde, to a condensation reaction withphenols, such as phenol, or with phenols substituted in the nucleus bychlorine atoms or C₁ -C₉ alkyl groups, for example 4-chlorophenol,2-methylphenol or 4-tert-butylphenol, or novolaks which can be obtainedby a condensation reaction with bisphenols, as described above.

(III) Poly-(N-glycidyl) compounds which can be obtained, for example, bydehydrochlorinating the reaction products of epichlorohydrin with aminescontaining at least two amino hydrogen atoms. Examples of these aminesare aniline, n-butylamine, bis-(4-aminophenyl)-methane,m-xylylenediamine or bis-(4-methylaminophenyl)-methane.

The poly-(N-glycidyl) compounds also include, however, triglycidylisocyanurate, N,N'-diglycidyl derivatives of cycloalkyleneureas, such asethyleneurea or 1,3-propyleneurea, and N,N'-diglycidyl derivatives ofhydantoins, such as of 5,5-dimethylhydantoin.

(IV) Examples of poly-(S-glycidyl) compounds are di-S-glycidylderivatives derived from dithiols, for example ethane-1,2-dithiol orbis-(4-mercaptomethylphenyl) ether.

(V) Examples of cycloaliphatic epoxide resins arebis-(2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentyl glycidyl ether or1,2-bis-(2,3-epoxycyclopentyloxy)-ethane.

It is also possible, however, to use epoxide resins in which the1,2-epoxide groups are attached to various heteroatoms or functionalgroups; these compounds include, for example, the N,N,O-triglycidylderivative of 4-aminophenol, the glycidyl ether/glycidyl ester ofsalicylic acid,N-glycidyl-N'-(2-glycidyloxypropyl)-5,5-dimethylhydantoin or2-glycidyloxy-1,3-bis-(5,5-dimethyl-1-glycidylhydantoin-3-yl)-propane.

Suitable epoxide curing agents (b) are acid, basic or catalytic curingagents. These include, for example, amines or amides, such as aliphatic,cycloaliphatic or aromatic, primary, secondary or tertiary amines, forexample hexamethylenediamine, N,N-diethylpropylenediamine,bis-(4-aminocyclohexyl)-methane,3,5,5-trimethyl-3-(aminomethyl)cyclohexylamine ("isophoronediamine"),2,4,6-tris-(dimethylaminomethyl)-phenol, p-phenylenediamine orbis-(4-aminophenyl)-methane; or polyamides, for example those formedfrom aliphatic polyamines and dimerized or trimerized unsaturated fattyacids; or polyhydric phenols, for example resorcinol,2,2-bis-(4-hydroxyphenyl)-propane or phenol/formaldehyde resins(phenol-novolaks); or boron trifluoride and its complexes with organiccompounds, for example BF₃ -ether complexes or BF₃ -amine complexes; orpolybasic carboxylic acids and anhydrides thereof, for example, phthalicanhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydrideor the corresponding acids.

Curing accelerators (c) can also be employed in the curing reaction;examples of such accelerators are tertiary amines or salts or quaternaryammonium compounds thereof, for example benzyldimethylamine,2,4,6-tris-(dimethylaminomethyl)-phenol, 1-methylimidazole,2-ethyl-4-methylimidazole, 4-aminopyridine, tripentylammonium phenate ortetramethylammonium chloride; or alkali metal alcoholates, for exampleNa alcoholates of 2,4-dihydroxy-3-hydroxymethylpentane.

Curable mixtures of this type can also contain suitable plasticizers,such as dibutyl phthalate, dioctyl phthalate or tricresyl phosphate, orreactive diluents, such as phenyl or cresyl glycidyl ether, butanedioldiglycidyl ether or hexahydrophthalic acid diglycidyl ester.

Finally, it is possible to add to the curable mixtures, in any phaseprior to curing, diluents, fillers and reinforcing agents, for examplecoal tar, bitumen, textile fibers, glass fibers, asbestos fibres, boronfibres, carbon fibres, mineral silicates, mica, powdered quartz,hydrated aluminum oxide, bentonites, kaolin or silica aerogel, or metalpowders, for example aluminium powder or iron powder, and also pigmentsand colorants, such as carbon black, oxide colours, titanium dioxide andothers. It is also possible to add to the curable mixtures othercustomary additives, for example flame-retarding agents, such asantimony trioxide, thixotropic agents and flow control agents, such assilicones, waxes or stearates (which in some cases are also used asmould release agents).

The preparation of the curable mixtures according to the invention canbe carried out in a customary manner by means of known mixing units(stirrers, kneaders, rollers etc.).

The curable epoxide resin mixtures according to the invention are used,in particular, in the fields of surface protection, electricalengineering, laminating processes and the building industry. They can beused in a formulation adapted in each case to suit the particularend-use, in an unfilled or filled state, as coating agents, paints, suchas sintered powder paints, compression moulding materials, dippingresins, casting resins, injection moulding formulations, impregnatingresins, adhesives, tooling resins, laminating resins, sealingcompositions, surface fillers, floor covering compositions and bindersfor mineral aggregates.

They can be used preferably as sintered powder paints, impregnatingresins and laminating resins, especially as impregnating and laminatingresins.

The curing of the copolymers, according to the invention, containingglycidyl groups is advantageously carried out within the temperaturerange from 50° C. to 300° C., preferably 80°-250° C.

Curing can also be carried out in a known manner in two or more stages,the first curing stage being carried out at a low temperature and thesubsequent curing at a higher temperature.

Curing can, if desired, also be carried out in two stages, by initiallydiscontinuing the curing reaction prematurely or carrying out the firststage at a rather low temperature, whereby a curable precondensate whichis still meltable and/or soluble (the so-called "B-stage") is obtainedfrom the epoxy component (a), the curing agent (b) and the, optionallypresent, accelerator (c). A precondensate of this type can be used, forexample, for the preparation of "prepregs", compression mouldingmaterials or sintered powders.

The term "curing", as used here, denotes the conversion of the solubleeither liquid or meltable, polyepoxides into solid, insoluble andinfusible, three-dimensionally crosslinked products or materials, as arule with simultaneous shaping to give moulded articles, such ascastings, mouldings and laminates, or impregnations, coatings, paintfilms and adhesive bonds.

The following examples illustrate the invention in greater detail.

PREPARATION EXAMPLES Preparation of the so-called advanced epoxideresins EXAMPLE 1 ##STR14##

502.60 g (1.20 mol) of the diglycidyl ether of4,4'-(cyclohex-3-en-1-yl-methylene)-diphenol (4.78 g equivalents/kg) and0.31 g of 2-phenylimidazole are initially placed in a 750 ml sulfonationflask equipped with an anchor stirrer, a reflux condenser and a droppingfunnel, and are heated to an internal temperature of 150° C. 168.22 g(0.60 mol) of 4,4'-(cyclohex-3-en-1-ylmethylene)diphenol are added inportions, with stirring, in the course of approx. 1 hour, thetemperature being kept below 170° C. Stirring is continued for a further2 hours at 150°-160° C., the hot melt is poured onto a metal sheet andcooled to room temperature, and the solidified resin is pulverized. Thisgives 632 g of a slightly coloured solid resin.

Elementary analysis: calculated (%): C 77.79, H 7.19; found (%): C76.99, H, 7.21.

Epoxide value: calculated: 1.88 equivalents/kg, found: 1.47equivalents/kg.

GPC (polystyrene standards)

4 main peaks

M_(w) =2590

M_(n) =1227

EXAMPLE 2 ##STR15##

416.80 g (1.20 mol) of bisphenol A diglycidyl ether, 168.21 g (0.60 mol)of 4,4'-(cyclohex-3-en-1-ylmethylene)-diphenol and 0.48 g of2-phenylimidazole are reacted in a 750 ml sulfonation flask by theprocess of Example 1. 561 g of a slightly coloured solid resin areobtained.

Elementary analysis: calculated (%): C 76.22, H 7.13; found (%): C75.88, H 7.11.

Epoxide value: calculated: 2.08 equivalents/kg; found: 1.79equivalents/kg.

GPC (polystyrene standards)

4 main peaks

M_(w) =4178

M_(n) =1354

EXAMPLE 3 Epoxidation of the product from Example 2 ##STR16##

528.66 g (0.55 mol) of the product from Example 2 in 2.0 l of chloroformare initially placed in a 4.0 l sulfonation flask equipped with athermometer, a stirrer, a cooler and an Impulsomat or Dosimat. 159.60 g(0.842 mol) of 40% peracetic acid are added dropwise at 35°-37° C. inthe course of 11/2 hours, the pH being kept constant (pH 4.0) with 20%NaOH. When the dropwise addition is complete, the reaction mixture isallowed to stand for approx. 4 hours more, to complete the reaction, andis then diluted with approx. 500 ml of chloroform, washed until neutralwith 1 l of 1N NaOH and 3×1 l of water, dried over Na₂ SO₄ and Na₂ SO₃and concentrated. Concentration and complete drying give 487.62 g(90.73% of theory) of a yellowish powder having an epoxide content of2.59 equivalents/kg (84% of theory).

EXAMPLE 4 Epoxidation of the product from Example 1

585.97 g (0.55 mol) of the product from Example 1 and 1,200 ml ofchloroform are initially placed in a 2.5 l sulfonation flask and arewarmed to 45°-50° C. 478.50 g (2.53 mol) of 40% peracetic acid are thenadded dropwise at 45°-50° C. in the course of 5 hours, with the pHcontrolled to a value of 4.0. When the dropwise addition is complete,the reaction mixture is allowed to stand for approx. 2 hours more, tocomplete the reaction, and is then diluted with approx. 500 ml ofchloroform, washed with 1 l of 1N NaOH and also with several times 1 lH₂ O, dried over Na₂ SO₄, freed from peroxides with Na₂ SO₃, filteredand concentrated. Concentration under a high vacuum (approx. 13 Pa) anddrying give 434.4 g of a yellowish powder having an epoxide content of3.34 equivalents/kg (74.39% of theory).

EXAMPLE 5 ##STR17##

47.17 g (0.10 mol) of the diglycidyl ether of4,4'-(3,4-epoxycyclohex-1-ylmethylene)-diphenol (epoxide groupcontent=6.37 equivalents/kg), 11.42 g (0.05 mol) of bisphenol A and 0.04g of 2-phenylimidazole are heated to an internal temperature of150°-160° C. in a 100 ml sulfonation flask equipped with an anchorstirrer, a thermometer and a reflux condenser, and are kept at thistemperature for 21/2 hours, with stirring. The clear yellowish melt ispoured onto a metal sheet and pulverized after it has solidified. 56.0 gof a slightly yellowish solid resin are obtained.

Elementary analysis: calculated (%): C 74.69, H 6.94; found (%): C72.39, H 6.89.

Epoxide group content: calculated: 3.41 equivalents/kg; found: 2.94equivalents/kg (86% of theory).

GPC (polystyrene standards)

M_(w) =6113

M_(n) =1351

EXAMPLE 6 ##STR18##

30.80 g of tetrabromobisphenol A (hydroxyl group content=3.68equivalents/kg), 42.50 g of bisphenol A diglycidyl ether (epoxide groupcontent=5.34 equivalents/kg), 26.70 g of the diglycidyl ether of4,4'-(3,4-epoxycyclohex-1-ylmethylene)-diphenol (epoxide groupcontent=6.37 equivalents/kg) and 0.08 g of 2-phenylimidazole are heatedto an internal temperature of 160° C. in a 250 ml sulfonation flaskequipped with an anchor stirrer, a thermometer, a reflux condenser andblanketing with N₂ inert gas, and are kept at this temperature for 61/2hours, with stirring. The clear, yellowish melt is poured onto a metalsheet and is pulverized after it has solidified. 93.96 g of a yellowishsolid resin are obtained.

Epoxide group content: calculated: 2.84 equivalents/kg; found: 2.38equivalents/kg (83% of theory).

GPC (polystyrene standards)

M_(w) =2258

M_(n) =932

Preparation of the intermediates for the so-called advancement reactionEXAMPLE a ##STR19##

280.40 g (1.0 mol) of 4,4'-(cyclohex-3-en-1-ylmethylene)-diphenol,1,110.40 g (12.0 mol) of epichlorohydrin and 150.00 g of isopropanol areinitially placed in a 2.5 l sulfonation flask equipped with a stirrer, areflux condenser, a thermometer and a dropping funnel, and are heated toan internal temperature of 70° C., with stirring. 224.00 g (2.80 mol) of50% NaOH solution are added dropwise in the course of approx. 2 hours,the temperature being kept at 70° C.-75° C. Stirring is continued for afurther 2 hours at 70° C. after the addition, the mixture is coded to20° C. and the reaction product (a somewhat smeary suspension) is washedwith twice 750 ml of 5% NaHSO₄ solution and once with 1,000 ml of water.The organic phase is dried over sodium sulfate, filtered and evaporatedin vacuo. 368.9 g of a clear, slightly coloured resin are obtained afterdrying in vacuo at 120° C./1.3 Pa (3 hours).

Elementary analysis: calculated (%): C 76.50, H 7.19; found (%): C75.67, H 7.24.

Epoxide value: calculated: 5.1 equivalents/kg; found: 4.7equivalents/kg.

EXAMPLE b Epoxidation of the product from Example a ##STR20##

333.63 g (0.850 mol) of the diglycidyl ether from Example a, of epoxidecontent 4.305 equivalents/kg, are initially placed, together with 680 mlof chloroform, in a 2.5 l sulfonation flask equipped with a stirrer, athermometer, a condenser, a pH meter, a pH electrode, a Dosimat and anImpulsomat. 246.50 g (1.292 mol) of 40% peracetic acid are addeddropwise in the course of 4 hours at a temperature of 40°-50° C., the pHbeing kept constant throughout at a value of 4.0. When the dropwiseaddition is complete, the reaction mixture is allowed to react for afurther hour and the aqueous phase is then separated off and the organicphase is neutralized with 2×500 ml of water and 1×250 ml of NaHCO₃,dried over Na₂ SO₄ and freed from peroxides with Na₂ SO₃, filtered andconcentrated in vacuo (50°-70° C./665-1330 Pa).

Drying leaves 316.0 g (91.01% of theory) of a colourless powder havingan epoxide content of 6.36 equivalents/kg and a viscosity of 5,835 mPasat 80° C. M_(n) /M_(w) =428/449.

IR (film): 3,500-3,200, 3,000-2,800, 1,600, 1,520, 1,240, 1,040 and 820cm⁻¹. NMR (CDCl₃): 0.8-2.5 m 9H (cyclohexyl-H), 2.5-4.0 m 11H (glycidylH2 methine-H), 6.8-7.2 d×d 8H (aromatic H).

Preparation of cyclohex-3-en-1-ylmethylenediphenol EXAMPLE A ##STR21##

1,129.3 g (12.0 mol) of phenol, 10.0 ml of 3-mercaptopropionic acid,76.0 g (0.40 mol) of toluene-4-sulfonic acid monohydrate and 600.0 ml oftoluene are initially placed, under inert gas blanketing, in a 4 lsulfonation flask, equipped with a stirrer, a reflux condenser, adropping funnel and a thermometer, and are stirred to form a solution.This is cooled to an internal temperature of +15° C. by means of an icebath, and 220.2 g (2.0 mol) of 1,2,5,6-tetrahydrobenzaldehyde are addeddropwise in the course of 1 hour, with such cooling that the internaltemperature remains at approx. +15° C. The cooling bath is removed andthe mixture is stirred for a further 6 hours at room temperature. Theresulting suspension is filtered, and the residue on the filter is driedin vacuo at 80° C.

424.8 g (yield=75.7%, calculated on tetrahydrobenzaldehyde employed) ofreddish-coloured cyclohexenylmethylenediphenol are obtained. 319.6 g ofcolourless product are left after recrystallization from 1,300 ml ofisopropanol (57% yield, relative to tetrahydrobenzaldehyde).

Melting point: 215°-216°.

Elementary analysis (recrystallized product): calculated (%): C 81.40, H7.19; found (%): C 81.02, H 7.21.

APPLICATION EXAMPLES

I. Phenolic curing (by means of cresol novolak)

The following formulations are used, as 65% solutions in DMF, to coataluminium sheets, which are then dried. The films thus obtained have adry film thickness of approx. 50 μm. The glass transition temperatureand the resistance to chemicals are determined after curing for 1 hourat 180° C.

    __________________________________________________________________________    Test    A              B              C                                       __________________________________________________________________________    Formulation                                                                           Product according                                                                      100                                                                              parts                                                                            Product according                                                                      100                                                                              parts                                                                            Product according                                                                      100                                                                              parts                               to Example 4   to Example 3   to Example 5                                    .sup.(1) Novolak                                                                        31                                                                              parts                                                                            Novolak   44                                                                              parts                                                                            Novolak   35                                                                              parts                               .sup.(2) EMI-2,4                                                                       1.4                                                                              parts                                                                            EMI-2,4  2.0                                                                              parts                                                                            EMI-2,4  1.6                                                                              parts                       Solution in                                                                           65%            65%            65%                                     DMF                                                                           Curing  1 hour at 180° C.                                                                     1 hour at 180° C.                                                                     1 hour at 180° C.                .sup.(3) T.sub.G                                                                      174° C. 185° C. 170° C.                          .sup.(4) Rubbing test                                                                 0              0              0                                       (20 ≦) acetone                                                         .sup.(5) Resistance to                                                        chemicals:                                                                    5N NaOH 0              0              0                                       5N H.sub.2 SO.sub.4                                                                   0              0              0                                       __________________________________________________________________________     As can be seen from the above Table, the cured resins exhibit high glass      transition temperatures and an excellent resistance to chemicals.             .sup.(1) Cresol novolak, hydroxyl group content = 8.3 equivalents/kg          .sup.(2) 2Ethyl-4-methylimidazole                                             .sup.(3) Glass transition temperature obtained by thermomechanical            analysis.                                                                     .sup.(4) Acetone rubbing test: 0-5                                            0 = film not attacked                                                         5 = film dissolved away                                                       .sup.(5) Resistance to chemicals: the effect of 1 drop on the film for 1      hour (at room temperature), followed by scratching with spatula               0-5                                                                           0 = film not attacked                                                         5 = film dissolved away                                                  

II. Powder paint

Preparation of samples: the components of the formulation shown in thefollowing table are ground and thoroughly mixed. The powder is appliedto a preheated aluminium panel (180° C.) so as to produce a filmthickness of 40-60 μm. The film is cured for 30 minutes at 180° C., andthe properties listed in the table are then determined.

As can be seen, the cured resins give coatings free from yellowing andhaving good mechanical properties and good resistance to chemicals. Thehigh reactivity of the resin mixture, which is reflected in a short geltime, is remarkable.

Notes

                                      TABLE                                       __________________________________________________________________________    Test           D               E               F                              __________________________________________________________________________    Formulation    Product according                                                                       145                                                                              parts                                                                            Product according                                                                       195                                                                              parts                                                                            Product according                                                                       175                                                                              parts                            to Example 4    to Example 3    to Example 5                                  Uralac 3400.sup.(1)                                                                     855                                                                              parts                                                                            Uralac 3400.sup.(1)                                                                     805                                                                              parts                                                                            Uralac 3400.sup.(1)                                                                     825                                                                              parts                            Accelerator.sup.(2)                                                                      20                                                                              parts                                                                            Accelerator.sup.(2)                                                                      20                                                                              parts                                                                            Accelerator.sup.(2)                                                                      20                                                                              parts             Gel time at 180° C. (minutes)                                                         2               2               2                              Curing (°C.)                                                                          180             180             180                            (minutes)       30              30              30                            Yellowing      colourless      colourless      colourless                     Erichsen impact indentation                                                                  <10             >180            >180                           (cm · kg)                                                            Erichsen indentation (mm)                                                                    <1              >10             >10                            Adhesion (0-5) Gt 0            Gt 0            Gt 0                           (cross-cut test)                                                              Acetone test (0-5) (1 minute)                                                                3-4             2-3             2-3                            Konig hardness (seconds)                                                                     208             218             216                            T.sub.g (°C.) (DSC)                                                                    84              85              88                            Differential thermogravimetry;                                                10°  C./minute                                                         T(-5%) (°C.)                                                                          370             370             365                            T(-10%) (°C.)                                                                         395             390             390                            T(-50%) (°C.)                                                                         460             450             460                            __________________________________________________________________________

III. Laminate (printed circuit board)

A 75% solution of the product from Example 6 in methyl ethyl ketone isprepared and is used to formulate an impregnating solution of thefollowing composition.

133.0 parts of 75% solution of the product from Example 6,

37.7 parts of 10% solution of dicyandiamide in methylglycol,

3.9 parts of 5% solution of benzylmethylamine in methylglycol and

29.0 parts of methylglycol.

A glass fabric (type 7628 CS, finish Z 6040) is impregnated with thissolution and is dried in a circulating air oven at 170° C. for 41/2minutes. The prepregs are then compressed, together with copper foil,for 2 hours at 170° C., using a pressure of 20-40 kg/cm², to givelaminates having the following properties.

Glass transition temperature T_(G) (DSC): 160° C.

Absorption of N-methylpyrrolidone: 0.0%

Pressure cooker test (1 hour): successful

Flammability (UL-94): V-O

What is claimed is:
 1. A compound of the formula I or II ##STR22## inwhich A is a radical ##STR23## R¹ is hydrogen or methyl, R² is theradical of an aliphatic, cycloaliphatic, aromatic or araliphatic diolafter both of the hydroxyl groups have been removed, R³, R⁴, R⁵ and R⁶independently of one another are hydrogen, C₁ -C₆ alkyl, chlorine orbromine, R⁷ is a radical of the formula III, IV, V or VI ##STR24## R⁸,R¹⁰, R¹² and R¹⁴ are hydrogen, C₁ -C₆ alkyl or phenyl, R⁹, R¹¹, R¹³ andR¹⁵ are hydrogen or C₁ -C₆ alkyl and the average value of n (numberaverage) is a number from 1 to 20, it being possible for the radicals R¹to R¹⁵, within a given molecule, to assume different meanings within thescope of the definitions given.
 2. A compound of the formula I or IIaccording to claim 1, in which R¹ is hydrogen.
 3. A compound of theformula I or II according to claim 1, in which R² is 1,2-phenylene,1,3-phenylene or 1,4-phenylene or radicals of the formula VII ##STR25##in which X is a direct C--C bond or is selected from the group ofradicals consisting of --CH₂ --, --CHCH₃ --, --C(CH₃)₂ --, --O--, --S--,--SO₂ -- or --CO--, m is an integer from 0 to 4 and R¹⁶ and R¹⁷independently of one another are C₁ -C₆ alkyl, chlorine or bromine.
 4. Acompound of the formula I or II according to claim 1, in which R² is aradical of the formula VIIa ##STR26## and R³, R⁴, R⁵ and R⁶independently of one another are hydrogen, C₁ -C₆ alkyl, chlorine orbromine, R⁷ is a radical of the formula III, IV, V or VI ##STR27## R⁸,R¹⁰, R¹² and R¹⁴ are hydrogen, C₁ -C₆ alkyl or phenyl and R⁹, R¹¹, R¹³and R¹⁵ are hydrogen or C₁ -C₆ alkyl.
 5. A compound of the formula I orII according to claim 1, in which the average value of n is a numberfrom 1 to
 10. 6. A compound of the formula I or II according to claim 1,in which R⁷ is a radical of the formula III or IV.
 7. A compound of theformula I or II according to claim 1, in which R7 is a radical of theformula V or VI in which R¹², R¹³, R¹⁴ and R¹⁵ are hydrogen.
 8. Acurable mixture containing(a) at least one compound of the formula I orII according to claim 1, (b) an amount of an epoxide curing agentadequate for curing the said mixture and (c) if appropriate, a curingaccelerator.
 9. A cured product obtainable from a curable mixture whichcontains(a) at least one compound of the formula I or II according toclaim 1, (b) an amount of an epoxide curing agent adequate for curingthe said mixture and (c) if appropriate, a curing accelerator, and whichis cured at a temperature from 50° C. to 300° C. in one, two or morestages, in the event of curing in two or more stages the first curingstage being carried out at a low temperature and the subsequent curingat a higher temperature, or the curing reaction being initiallydiscontinued prematurely, or the first stage being carried out at arather low temperature, so that a "B-stage" precondensate is initiallyformed from the components (a), (b) and, if appropriate, (c) and this isnot cured completely until later at a higher temperature.